SK216292A3 - Multilayer foil with improved barrier effect for gases - Google Patents
Multilayer foil with improved barrier effect for gases Download PDFInfo
- Publication number
- SK216292A3 SK216292A3 SK2162-92A SK216292A SK216292A3 SK 216292 A3 SK216292 A3 SK 216292A3 SK 216292 A SK216292 A SK 216292A SK 216292 A3 SK216292 A3 SK 216292A3
- Authority
- SK
- Slovakia
- Prior art keywords
- water
- film
- impermeable
- gas barrier
- pval
- Prior art date
Links
- 230000004888 barrier function Effects 0.000 title claims abstract description 50
- 239000007789 gas Substances 0.000 title claims description 53
- 239000011888 foil Substances 0.000 title claims description 34
- 230000000694 effects Effects 0.000 title claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 31
- 239000012790 adhesive layer Substances 0.000 claims abstract description 27
- 239000004014 plasticizer Substances 0.000 claims abstract description 19
- 229920003023 plastic Polymers 0.000 claims abstract description 18
- 239000004033 plastic Substances 0.000 claims abstract description 18
- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000004806 packaging method and process Methods 0.000 claims abstract description 5
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- 238000010030 laminating Methods 0.000 claims abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- -1 aliphatic polyols Chemical class 0.000 claims description 21
- 239000010410 layer Substances 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 235000013305 food Nutrition 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 241000251468 Actinopterygii Species 0.000 claims description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 230000035515 penetration Effects 0.000 claims description 3
- 230000035699 permeability Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims description 3
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 235000016213 coffee Nutrition 0.000 claims description 2
- 235000013353 coffee beverage Nutrition 0.000 claims description 2
- 239000002537 cosmetic Substances 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
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- 239000003974 emollient agent Substances 0.000 claims description 2
- 235000019688 fish Nutrition 0.000 claims description 2
- 235000013332 fish product Nutrition 0.000 claims description 2
- 235000021022 fresh fruits Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
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- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
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- 229930003231 vitamin Natural products 0.000 claims description 2
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- 229920003176 water-insoluble polymer Polymers 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 239000002390 adhesive tape Substances 0.000 claims 1
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- 238000000071 blow moulding Methods 0.000 claims 1
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- 238000007710 freezing Methods 0.000 claims 1
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- 238000002386 leaching Methods 0.000 claims 1
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- 239000004821 Contact adhesive Substances 0.000 abstract 1
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- 230000009477 glass transition Effects 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 75
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 150000002763 monocarboxylic acids Chemical class 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920002689 polyvinyl acetate Polymers 0.000 description 6
- 239000011118 polyvinyl acetate Substances 0.000 description 6
- 239000013039 cover film Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 150000001408 amides Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- NQQRXZOPZBKCNF-NSCUHMNNSA-N (e)-but-2-enamide Chemical compound C\C=C\C(N)=O NQQRXZOPZBKCNF-NSCUHMNNSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AYMZQSQRCFSZCR-UHFFFAOYSA-N 1-(3,3-dimethylbutoxy)-3,3-dimethylbutane Chemical compound CC(C)(C)CCOCCC(C)(C)C AYMZQSQRCFSZCR-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- TYIUEFYPIHUHTD-UHFFFAOYSA-N 4-ethylhexyl prop-2-enoate Chemical compound CCC(CC)CCCOC(=O)C=C TYIUEFYPIHUHTD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000132092 Aster Species 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- ABBZJHFBQXYTLU-UHFFFAOYSA-N but-3-enamide Chemical compound NC(=O)CC=C ABBZJHFBQXYTLU-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
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- 239000003085 diluting agent Substances 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
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- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 238000003475 lamination Methods 0.000 description 1
- 238000011866 long-term treatment Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
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- 229920001521 polyalkylene glycol ether Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical class CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 238000007761 roller coating Methods 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/31721—Of polyimide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/31855—Of addition polymer from unsaturated monomers
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- Y10T428/31913—Monoolefin polymer
- Y10T428/3192—Next to vinyl or vinylidene chloride polymer
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Abstract
Description
Vynález ee týtyá termoplastický . formovalelnýoh fólií vzniklých spojením nškolika vr3tev, se zlepšeným berie r o výra účinkem pro plyny. Tyto fólie sestávají z alespoň jedná barierové fólie pro plyny na búzi polyvinylalkoholu (PVAL) s nejménš jednostrannou, s výhodou oboustrannou krycí fólií z plastické hmoty, která je nerozpustná ve vodš a popri pad ž nerozpustná v organických rozpuätédlech, pŕičemž tato krycí fólie je celoplošné pomoci zvlášní adhezní vrstvy aleapojŕ jednostranné, a výhodou oboustrannš kašírována na barierové fólii pro plyny. Barierové fólie pro plyny obsahují vysokovroucí PVAL a vícevrstvé fólie mají, ve srovnání s dosavadním stavení techniky, zlepšený barierový účinek pro plyny, zvlášté účinek proti kyslíku a proti aromatickým látJ kám, stejnš jako výhodné mechanické vlastnosti.The invention relates to thermoplastic. moldable films formed by combining several layers with improved gas efficiency. The films comprise at least one polyvinyl alcohol gas barrier film (PVAL) having at least one, preferably two-sided, plastic cover film which is insoluble in water and, where appropriate, insoluble in organic solvents, the cover film being a full-surface aid The separate adhesive layers are preferably one-sided and preferably double-sided laminated on a gas barrier film. The gas barrier films contain high-boiling PVAL and the multilayer films have, compared to the prior art, an improved gas barrier effect, a particular action against oxygen and aromatics as well as advantageous mechanical properties.
Doaavadní stav technikyBACKGROUND OF THE INVENTION
Vícevrstvé fólie s dobrými barierovými vlastnostmi pro plyny jsou již známé a mnohostranné se používaj! jako balící fólie. Takové fólie obBahují jako bariéry pro plyny e výhodou fólie na bázi kopolyméru ethylenu s vinylalkoholem s krycími foliemi, které jaou nerozpustné ve vodš (srovnej evropský patentový spia č. 0 118 060). Barierový účinek téchto fólií pro plyny, napríklad proti kyslíku, je vštšinou horší než 5 cmvw^-Äbar, stanoveno podie normy DIN 5 3 380, pri relatívni vlahkoeti vzduchu co pro radu použití nepostačuje.Multilayer films with good gas barrier properties are already known and versatile! as packaging foil. Such films include, as gas barriers, preferably films based on an ethylene-vinyl alcohol copolymer with cover films which are water-insoluble (cf. European Patent Specification 0 118 060). The barrier effect of these foils for gases, for example against oxygen, is generally inferior to 5 cm / cm @ 2 -bar, determined according to DIN 5 3,380, with a relative humidity of air which is not sufficient for many applications.
Výroba vícevrstvých fólií ae obecné provádí koextrudaôními zpúsoby za kaôírování koextrudovaných jednotlivých fólií na požadovanou opojenou fólii za použití proatŕedku umožňujícého spojení,napríklad ionomeru nebo modifikovaného polyolefinu.The production of multilayer films and, in general, is carried out by coextrusion processes, by co-extruding the coextruded individual films to the desired intoxicated film using a bonding agent such as an ionomer or modified polyolefin.
Použití bôžného polyvinylalkoholu (PVAL) jako barierové fólie pro plyny je rovnčž jlž známo a môže véat ke zlepšeným barierovým účinkôm pro plyny, ve arovnání napríklad a použitím svrohu uvedených a relativnč drahých kopolymerô ethylenu a vinylalkoholem. Tyto fólie ae dají v3ak bez pŕíeady zmékčovadla sn-ádno extrudovat a koextrudovat, v protikladu k obvyklým polyvinylalkoholôm, které aé dají formovat a extrudovat pouze obtížnS a za značného prídavku zmékčovadla nŕi termoplastických podmínkách. Kromé toho se PVAL fólie nemohou termoplastioky 3pojovaž nebo kašírovat s obvyklými krycími foliemi nerozpustnými ve vodé, které tvorí nep&iární polyméry, napríklad polyolefiny, jako je polyethylen nebo pojlypropylen, nebo polyvinylchlorédem nebo polyvinylidenchloridem bez použití vázaoích múatkú, takže opojené fólie s PVAL foliemi až doaud se používaly pouze ojedinôle. Z evropského patentového spisu c. 0 O8o 664 je znám zvláätní zpôaob extdudace pro výrobu plochých nfedmétú a prvku z vétfiího ροδ-t a polymeračním stupném Ϊ)Ρ^ od 250 do 3000. Pritom ae jak pro fotopolymemí tlakové deaky, tak také r>ro jiné účely používá částečnč zmýdelnéného polyvinylacetátu ae stupném zrnýdelnéníThe use of conventional polyvinyl alcohol (PVAL) as a gas barrier film is also known and can lead to improved gas barrier effects, as compared to, for example, and the use of the abovementioned and relatively expensive copolymers of ethylene and vinyl alcohol. However, these films can easily be extruded and coextruded without the addition of plasticizer, as opposed to conventional polyvinyl alcohols, which can only be formed and extruded with difficulty and under considerable thermoplastic conditions. In addition, PVAL films cannot be bonded or laminated with conventional water-insoluble coating films that form non-polar polymers, such as polyolefins such as polyethylene or polypropylene, or polyvinylchloride or polyvinylidene chloride without the use of PV bonding agents, so that the PVAL films are embedded used only sporadically. From European Patent Specification c. A special method of extuding for the production of flat articles and elements of the greater degree of polymerization degree from 250 to 3000 is known in the art. It is known that for both photopolymers pressure contacts and also for other purposes it uses partially saponified polyvinyl acetate; gradual grain
.. 3 do 500. Jejich termoplastioké zpracování se provádí bez, predoházejíoí separační predplastifikace pŕímo v dvouänekovém extrudačním stroji a. výsledné PVAL fólie rnají být vhodné také pro výrobu laminátú nebo spojených desek. K tomu se mají polyvinylalkoholové fólie buď na jedné nebo na obou stranách nakaéírovat na válcovací stolici dážéí fólií, napríklad z jiné plastická hmoty nebo kovové plechové vrstvy a to bez použití mezivrstvyr Pritom se váak ukazuje, že tímto zpúsobem se nemúže dosáhnout uspokojivého vnitŕního spojení mezi PVAL fólií a nakaäírovanou fólií z jiné plastické hmoty a kromé toho Částeóným zmýdelnéním PVAL se také prakticky nemúže dosáhnout podstatného zlepšení barierových vlastností pro plyny, ve srovnání s dosavadním atavem techniky. ČástečnS zmýdelnéné polyvinylalkoboly jeou jako materiály barierových fólií pro plyny inéné vhodné a barierový úéinek pro plyny se u tociito fólií zhoršuje značným prijmem vody.3 to 500. Their thermoplastic treatment is carried out without, but not precluding, separating preplastification directly in a twin-screw extruder. the resulting PVAL films are also suitable for the production of laminates or bonded sheets. For this purpose, the polyvinyl alcohol foils are to be coated on one or both sides with a rain foil, for example of a different plastic or metal sheet, without the use of an intermediate layer. However, this shows that a satisfactory internal connection between the PVAL cannot be achieved. In addition, with partially plasticized foil and coated foil of other plastics, a partial improvement of the saponification PVAL also practically fails to achieve a substantial improvement in the gas barrier properties compared to the prior art. Partially saponified polyvinyl alcohol is another suitable gas barrier film material and the gas barrier effect of these films is deteriorated by considerable water uptake.
Tento vynález s© klade za úkol ziskat použitelné', vícevrstvé fólie se zlepäeným barierovým dčinkem pro plyny za použití cenové pŕíznivé dostupného PVAL jako barierové folée pro plyny, které nemají uvedené nedostatky u dají se vyrobit jednoduše a za pŕíznivých cenových, relací.SUMMARY OF THE INVENTION It is an object of the present invention to provide useful multilayer films with improved gas barrier effect using cost-effective PVAL as a gas barrier film which do not have the above drawbacks and can be manufactured simply and at favorable cost.
Podstata vynálezuSUMMARY OF THE INVENTION
S prekvapením bylo nyní nelezeno, žo použitím vyeokovroucíoh polyvinylalkoholú v barierových foliích pro plyny se múže dosáhnout značného ^výšení barierováho účinku pro plyny s s tím se múže docílit vnitŕního spojení PVAL barierových fólií pro plyny a krycíah fólií z plastické hmoty ne rozpustné v© vodé a že tyto krycí delie z plastické hmoty nerozpustné ve vodé se mohou nakaéírovat ze. použití zvláštni lepiči adhezní vrstvy na PVAL fólie. Zvláété výhodné se pritom použivá extrudovaných vyfukovaných fólií obaahujících zmékčovadlo, které ^gou z vysoce zmýdelnéných polyvinylalkoholú, které máji prúmémý nolywrační etupeň .yy^äí ne Ž 1500.Surprisingly, it has now been found that by using high-boiling polyvinyl alcohols in gas barrier films, a considerable increase in the gas barrier effect can be achieved with the result that the internal bonding of the PVAL gas barrier films and the plastic foil cover and not soluble in water can be achieved. these water-insoluble plastic cover portions can be coated. use of a special adhesive adhesive layer on PVAL films. Particularly preferred are extruded blown films containing a plasticizer, which are made of highly saponified polyvinyl alcohols having a rectangular polyolefinic degree of less than 1500.
Pŕedmé.tem vynálezu jsou tudíž víoevratvó fólie, která jsou termoplasticky formovatelné, ae zlepšenýmit barierovýmj účinkem pro plyny, seetávajíoí z alespoň jedné barierové fólie pro plyny na bázi PVAL, která je z jedné strany nebo z obou straň kaéírovány s polymemí fólií nerozpustnou ve vodé a popŕipadé nerozpustnou v organických rozpouétédlech, jako vrstvou zabranující pronikání vody a vodní páry, pŕičemž vícevrstvé fólie mohou také obsahoval včtčí počet etejných nebo nižných barierových fólií pro plyny, a polymemími foliemi uloženými mezi nimi k zabránení pronikání vody a vodní ; páry, které se vyznačuj! tím, že barierové fólie pro plyny obsahuj! vysoce zmýdelnčný PVAL a jsou kašírovány jednoetranné·/ nebo obouatranné, s výhodou oboustranné, s polyraerní fólií nebo polymemími foliemi, které je nebo které jsou nerozpust- \ né ve vodé, nepropuetné pro vodu nebo vodní páru a popŕipadé nerozpustné v organických rozpouštédlech, pŕičemž mají pŕea adhezní vrstvu lepiči vlastnosti a jsou pro vodu nebo vodní páry neprestupné.Accordingly, the present invention provides multi-return films that are thermoplastically formable and improve the gas barrier effect from at least one PVAL gas barrier film that is coated on one side or both with a polymer film insoluble in water and optionally insoluble in organic solvents, such as a water and water vapor barrier layer, wherein the multilayer films may also contain a plurality of same or lower gas barrier films, and polymer films interposed therebetween to prevent water and water penetration; pairs that distinguish themselves! in that the gas barrier foils comprise! highly saponifiable PVAL and are laminated unilateral and / or bilateral, preferably two-sided, with a polymeric sheet or polymeric foils which is or is insoluble in water, impermeable to water or water vapor, and optionally insoluble in organic solvents, having the adhesive layer has adhesive properties and is impermeable to water or water vapor.
Barierové fólie pro plyny mají s výhodou tlouštku vrstvy v razmezí od 10 do 100 zvláété od 40 do 60 ^im, obzvláétč výhodné od 45 do 55/um. Tyto fólie s výhodou obsahují vysoce zmýdelnšn^ 'PVAL, jehož esterové čísi® Činí méné nežThe gas barrier films preferably have a layer thickness ranging from 10 to 100, in particular from 40 to 60 µm, particularly preferably from 45 to 55 µm. These films preferably contain a high saponification PVAL whose ester number is less than
- 5 10 mg KOH/g, stupeň zmýdelnéní . je .·νθ.ΐ’§ί než98. zbytkový obsah acetylových ekupin je menší · než. (1 .^.hmotnoetní a s výhodou, strední 1¾. je wé&ňí než 1500, vztafceno ,yž^y.jna PVAL. tíakŕorové fólie, pro. plyny .obsahuj í dále.e výhodou·. až5. 50 $lunotnoBtníoh,... zvláätč 12 .až 20,$. bmptnps^íoh.t;.5.^ifj^.$ir kého polyolu se 2-.až.-.6 atómy uhlíku nebo. oligomarní]hoA.poljyalkylenglykoletherpolyolu ae 2 až 6 atómy, uhlíku· v, alkyle^y.é části,,. a výhodou glycerínu jako amekčo,vadia PVAí» :pŕiéemž zmékčovadlo .«á a výhodou* odpovídat. predpisu .pro, balení' potravín, popŽ'ípadÉ až 5 A hino.tnoatníoh vody, ,.popŕipadé- až s12 hmotnoatních proBtŕedku .usnadňu jícího* tečení ,.a popŕipadé » výhodou až rL ý>.· hmotnoetní antiblokovaoího prostŕedku,,' pŕičemž ... rvšechny údaje jsou· vstaženy na ŕVAL. is · ‘ Jí ·á,'· ?á·..: t·.- 5 10 mg KOH / g, saponification degree. is. · νθ.ΐ'§ί than98. the residual acetyl content is less than. ( 1) by weight, and preferably, the mean 1 'is greater than 1500, based on PVAL three-layer foils for gases, and further preferably has up to about 5 % by weight. . .When zvláätč 12 20 $. bmptnps IOH ^. t; .5. ^ ifj ^. $ ir Kehoe polyol 2 .When-.-., or 6 carbon atoms. oligomarní] to .poljyalkylenglykoletherpolyolu and e 2 to 6 carbon The alkyl moiety and preferably the glycerol such as ammonium will have a plasticizer, and preferably the plasticizer will comply with the food packaging regulations and possibly up to 5%. The composition may contain up to 12% by weight of the flow aid and preferably up to about 12% by weight of the antiblocking agent, all of which is based on VAL. She · '· á ..: t ·.
·:·. . Barierové fólie pro plyny ..jsou ,a výhodou <.pyAL·-.. extrudované. vyfukovaná .fólie obealiující,, zmékčpyadlg,.;tex^opplasticky formované o šobä znárným zpúeobem., která obqahují. Od.5 do 50 -Λ .htoQtnostní.ch, s výhodou od 12 do . 2.0. ^.hmotnost^.ÍQh^ alifatických polyold se 2 až 6 atómy uhlíkune,bo oligomemíoh polyalkylang.lykolether.polyolú ae 2 až 6 atómy, uhlíku y alkylenové Části, 3 výhodou glycerínu .·jako žmékčovadla ua>.až ;-5..$7^ hmotnostnícu vody, vztažoľio vždy, na . PVAL, jakož ,i popŕipadé daläí pomocné .zpracovatelské prostŕedky» jako jsou ppostredky ušnadňujíoí tečení a.antiblokovací prostŕedky. Ježádoucí, aby ŕVAh extrudované vyfukované fólie a e. po. výroby .a pŕad,^ ... svým delším zpracováním na.apojené fólie neohyly tvarové .ustálil obvyklým , zpúeobern temperováním .na teplotu.,80. °Cva. piŕi zvýšené® obsahu vody .neohaly vysuš i t na obsah; vody, nižší... než • 5 /· hmotnostních,” .. vataženo na PVAL. > ?· \ «„A·-, ' ' ; *' ·<. ’ •’-í.ntť'VŽitnC „· ·. . The gas barrier films are, and preferably are, extruded. a blown film encircling the softening material, which is opplastically formed in a manner known in the art, which comprises. From 5 to 50% by weight, preferably from 12 to 50% by weight; 2.0. The weight of aliphatic polyols having 2 to 6 carbon atoms or oligomeric polyalkylene glycol ether polyols and 2 to 6 atoms, carbon atoms and alkylene moieties, preferably glycerol, as a plasticizer at a radical of up to 2 ; % By weight of water, in each case per. PVAL as well as, if desired, other processing aids such as flow facilitators and anti-blocking agents. Desirably, extruded blown film and e. after. For the production of the film, the long-term treatment of the bonded films did not stabilize the shape in the usual manner by tempering to the temperature of 80 ° C. ° C at a. at elevated water content, could not dry to content; water, lower ... than • 5 / · by weight, ”..plated on PVAL. >? · \ «„ A · -, ''; * '· <. '•'-í.ntť'VŽitnC'
Jako výchozí ’PVAL pŕivházející v úvahu pro výrobu barierových fólií pro plyny, použiteľných podie tohoto vynálezu, jsou vysoko molekulám! typy P VAL s číslem smýdelňéní e výhodou vyšéím než 98 j' molárních, a£ do 100 $ molámích, jako jsou napríklad ľVAL získatelné aydrolýzou nebo alkoholýaou vysoko molekulámích esteru kyselín polyvinylkarboxylovýoh, s výhodou polyvinylaoetátu nebo polyvinylpropionátu, zvlášté výhodné polyvinylaoetátu. Vhodnými obchodné dostupnými tyyy P VAL jsou napríklad (H^owiol typú 20-98, 28-99» §6-98 a 66-100 firmy Hoechst AG. Zvlášté výhodné jsou Mowiol 28-99 a lfowiol 66-100.Poly vinylalkoholy se e výhodou termoplasticky spracovávaj! ve fomé obsahující začkčovadlo a v extinmé pŕedplastifikovaných tak zvaných suchých smésích. Výraze® suohá smés se rozumíC2±^^?£^Sf:ľ7ý3ľ''3“ smési z PVAL, zmlkčovadla, vody, prostŕedkú uenadňujíáího tečení a antiblokovacího prostŕedkú, pŕedgranulované a pŕedplastifikované v zaŕizení s nuceným mí chánim v oddéleném pracovní m stupni za teploty až do 120 °C. Tyto suché smési se bez problému extrudují a nechají fonnovat na extrudovrié vyfukované fóliej pritom podíl zmékčovadla a vody se stanoví tak, že teplota tavení suché smési je pod teplotou rozkladu polyvinylalkoholú, takže pri extrudován$he«úže naetat termický rozklad polyvinylalkoholú (srovnej evropský patentový spis S.As the starting PVALs contemplated for the production of gas barrier films useful in the present invention, they are highly molecules. P VAL types having a saponification number of preferably greater than 98 mole% and up to 100 mole%, such as ľVAL obtainable by hydrolysis or alcoholization of high molecular weight polyvinyl carboxylic acid esters, preferably polyvinyl acetate or polyvinyl propionate, particularly preferred polyvinyl acetate. Suitable commercially available P VALs are, for example, (H- owiol types 20-98, 28-99, §6-98 and 66-100 from Hoechst AG. Mowiol 28-99 and lfowiol 66-100 are particularly preferred. preferably thermoplastically processed in a form containing a starter and extensively pre-plasticized so-called dry blends. pre-granulated and pre-plasticized in a forced-mixing apparatus in a separate working stage at a temperature of up to 120 ° C. These dry mixtures are extruded without difficulty and allowed to form on the extruded blown film, the proportion of plasticizer and water being determined so that the melting point of the dry mix is below the decomposition temperature of the polyvinyl alcohols, so that during the extrusion process, the thermal decomposition of the polyvinyl alcohols can cure (cf. European Patent Specification S).
004 5&7). Jako prostŕedek uemadňující tečení obsahují suché smési s výhodou 2 až 20 $ hmotnostních, zvlášté 7 až 12 $ hmotnostních práškového polyméru, který s výhodou tvorí polymér nerozpustný ve vodé, zvláčtδ rozstŕikováním vysušeného disperzního práškového polyvinylaoetátu (napríklad prášku (^Mowilitti 03,práškového polyvinylaoetátu znovu dispergovatelného ve vodé, firmy ^oeohst AG.). 3uohé smési jako antiblokovací prostŕedek s výhodou obsahují 0,1 až 1 ň hmotnostní, zvlášté 0,3 až 0,9 % hmotnostního, vztaženo vždy na PVAL, vyaoce disperzní kyseliny kremičité (napríklad ^Aeroail firmy Deguaaa) nebo kyseliny stearová» 3 výhodou se PVAL fólie obsahujioí zmékčovadlo, získatelné ze suchých smési vyfukovaoí extrudací, po své výrobé a pred dalším zpracovánía zpúsobem podie tohoto vynálezu na barierové fólie pro plyny vysuší na obsah vody menší než 5 % hmotnostníoh, vztaženo na PVAL, a kronté toho nechájí tvarové ustálit, napríklad w teoerováňíiä sa teploty 80 °0.004 5 & 7). As a flow-promoting agent, the dry mixtures preferably comprise from 2 to 20% by weight, in particular from 7 to 12% by weight, of a powdered polymer which preferably consists of a water-insoluble polymer, in particular by spray-drying dispersed powdered polyvinyl acetate (e.g. The water-dispersible mixtures according to the invention are preferably 0 to 1% by weight, in particular 0.3 to 0.9% by weight, based on PVAL, of highly disperse silicic acid (e.g. Aeroail of Deguaaa) or stearic acid, preferably, the PVAL film comprises a plasticizer obtainable from the dry blend by extrusion blow molding, after its manufacture and before further processing and process according to the invention to gas barrier films, to a water content of less than 5% by weight. on PVAL, and not that it maintains the shape steady, for example at a temperature of 80 ° 0.
Jako zmékčovadlo se pro PVAL pouŽívá zvlášté glycerín, stejné jako kombinace glyoerinu a vody. Vhodnými zmékčovadly jsou dále sloučeniny, jejich smési nebo jejich kombinaoe s vodou, popŕipadé jejich kombinace s glycerínom a vodou, pŕičemž se mohou použít látky ze souboru zahrnujícího termoatabilní alifatické oligomerní ethery diolú se 2 až 6 atómy uhlíku, s výhodou až s 10 alkylenoxidovýai základními jednotkami v molekule, zvlášté alkylenglykoly se 2 až 6 atómy uhlíku v alkylenu nebo alkandioly se 2 až 6 atómy uhlíku, a výhodou oligomerní ethery ethylegtykolu, propylengjfcykolu, butylenglykolu, smíšené ethery téchto glykolú, zvlášté diethylmnglykol, triethyfiiglykol, tetraethylenglykol a pentaethylenglykol. Také jednoduše etherifikované alkylengj^koly se 2 až 6 atómy uhlíku nebo alkandioly a© 2 až 6 atómy uhlíku se mohou používat, zvlášté pak ethyfhglykol, propyľftiglykol a butyl englykol.A separate glycerin is used as a plasticizer for PVAL, as is the combination of glyoerin and water. Suitable emollients are furthermore compounds, mixtures thereof or mixtures thereof with water or combinations thereof with glycerol and water, and thermoatable aliphatic oligomeric diol ethers having from 2 to 6 carbon atoms, preferably up to 10 alkylene oxide base units, may be used. in the molecule, especially alkylene glycols having 2 to 6 carbon atoms in the alkylene or alkanediols having 2 to 6 carbon atoms, preferably the oligomeric ethers of ethylene glycol, propylene glycol, butylene glycol, mixed ethers of these glycols, especially diethylene glycol, triethylene glycol, and triethylene glycol. Simple etherified C 2-6 alkylene glycols or alkanediols and C 2-6 carbon atoms can also be used, in particular ethyl glycol, propylphiglycol and butyl englycol.
Míato použití suchých smési PVAL se také mohou používat práškové a granulovaná formy PVAL v pŕísluéném extruderu, napríklad v extruderu s dvojitým šnekem, nebo v extruderú opatŕenóm vhodným zaŕízeníiti pro mísení a plastifikaci, a zde pŕírno míslt a plaatifikovat s potrebným množstiifca zmékČovadla, vody a popŕipadé prostŕedku asnadňujícího tečení a popŕipadé antiblokovacího prostŕedku a teplota tavení smési ae líra upraví pod teplotu rozkladu PVAL. S výhodou se väak u vysoce zmýdelnéných a vysoko molekulámích polyvinylajkftoholi používá externé plastifikovanýoh suchých smési PVAL obsahujících zmékéovadlo.Instead of using dry PVAL mixtures, powdered and granulated forms of PVAL can also be used in the respective extruder, for example in a twin-screw extruder, or in an extruder provided with suitable mixing and plasticizing equipment, and here to mix and plaatify with the required amount of water and softener. a flow aid and optionally an anti-blocking agent; and the melting point of the mixture is adjusted to below the PVAL decomposition temperature. Preferably, however, external plasticized PVAL dry blends containing a plasticizer are used in highly saponified and high molecular weight polyvinyl alcohols.
Výroba fólií se s výhodou provádí pomoci jednošnekového vyfukovacího extruderu se zaŕízením pro dávkování suché smési PVAL obsahující zmékSovadlo a výsledná fólie ve tvaru vyfouknuté hadice se po ochlažení na teplotu místnosti a naŕíznutí v podéIném sméru vede pŕes zaŕízení k ukládání ploché fólie a potá na nanášeoích válcích oboustrané opatruje lepíoí adhezní vrstvou. Po vysušení lepíoí adhezní vrstvy v suéícŕ&aŕízení kanálového tvaru, kde pri zvýšené teploté se eoudasné nechá vysuéit barierová roli© pro plyny a Jepící adhezní vrstva, ee fólie nechá tvarové ustálit* Potom se takto získaná samolepící barierová fólie pro plyny kaéíruje pomoci kaší rovaoích válcú nebo na kalandru za teploty míatnosti z obou straň krycí fólií z plastické hmoty, která je nerozpustná ve vodé a nepropustná pro vodu, stejné jako pro vodní páry, na fólii spojenou z víoe vrstev, která je neprostupná pro vodu a pro plyny a která pri použití krycí fólie z plastické hmoty, která je nerozpustná v organických rozpouátédlech, je také neprestupná pro rozpuätédla.Barierová fólie pro plyny se popŕipadé kašíruje pouze z jedné strany krycí fólií z plastické hmoty, která je nerozpustná ve. vodé a nepropustná pro vodu, stejné jako pro vodní páry apopŕípadé nerozpustná v rozpouétédlech a lepiči adhezní vrstvaThe film is preferably made using a single screw blow extruder with a PVAL dry blend dispensing device containing the plasticizer, and the resulting blown tubing film is cooled through room temperature and longitudinally sliced through a flat film deposition device and sweats on two-sided rollers. provided with an adhesive layer. After drying of the adhesive layer in the channel-shaped dryer, where the gas barrier is allowed to dry at elevated temperature and the adhesive layer is allowed to form, the foil is then molded by means of slurry rolls or a calender at a temperature of both sides of a plastic foil which is insoluble in water and impermeable to water, the same as for water vapor, to a film connected from a plurality of layers, which is impermeable to water and gases, and which when using a foil The gas barrier film is optionally laminated on only one side with a plastic insoluble film that is insoluble in the solvent. water and impermeable to water, same as for water vapor and possibly insoluble in solvents and adhesive adhesive layer
a. Q — na druhé strané barierové fólie pro plyny ae pokryje odôtranitelný® pruhem ailikonovaného papíru, aby ae spojené fólie pozdéji, po.odstranéní krycího papíru, mohly použit pro výrobu laminátú a spojených deahte jednostranným nakaéírováním na odpovídajíoí podklad. Také časové omezené oboustranné pokrytí obouatranných lepiči ch adhezních vrstev, naoházejících se na barierové fólii pro plyny, allikonovým oddélovacím papírem nebo krycím papírem je možné až do pozdéjäího použití ke kašírování vícevratvé fólie.a. Q - on the other hand, the gas barrier films and e covers the removable strip of ailiconized paper so that the bonded films later, after removing the backing paper, can be used to make laminates and bonded by one-sided bonding to a corresponding substrate. Also, time limited two-sided coverage of the two-sided adhesive adhesive layers cast on the gas barrier foil, allicone separating paper or overlay paper is possible until later used to laminate the multilayer film.
Adhezní vrstva a lepícími vlastnostmi, označovaná zkrácené jako lepiči adlae’hí vrstva v pŕedcháze jíoím i v následujíoím textu, sestává s výhodou z kopolymerú, jehož teplota tuhnutí Tq je v rozmezi od -50 do -10 °C, méfeno pomoci diferenciální teplotní analýzy §DTA) a ve spojitosti 8 formou vrstvy je nepropustný pro vodu,atejné jako takŕka nepropustný pro vodní páry a nerozpustný ve vodé. Lepiči adhezní vrstva je a výhodou nanesená na barierové fólii pro plynu obsahujíví PVAL na jedné nebo na obou stranách a sice nastŕíkáním, nanesenám válci nebo stíráním z roztoku kopolymerú v organickém rozpouätčdle nebo z vodné disperze kopolymerú nebo z taveniny kopolymerú pri zpúsftbu v taveniné za horká, stejné jako popŕipadé v následujícím vysušení za odpaŕování roz- v 1 poufítédla nebo vody, pŕičemž sušení se múže současné apojit a tvarovým ustálením temperaoí PVAL vyfukované fólie obsa- '·>ŕ hujíoí zmékčovadlo, napríklad za teploty 80 °C. Tlouétkaf lepiči adhezní vrstvy je a výhodou v rozmezi od 20 do| um, zvláôté od 30 doThe adhesive layer and adhesive properties, referred to abbreviated as adhesive adhesive layer in the preceding and subsequent text, preferably consist of copolymers whose pour point Tq is in the range of -50 to -10 ° C, as measured by differential temperature analysis. and in connection with the layer 8, it is impermeable to water, the same as being almost impermeable to water vapor and insoluble in water. The adhesive adhesive layer is preferably applied to the gas barrier film containing PVAL on one or both sides by spraying, roller coating or wiping from a solution of copolymers in an organic solvent or from an aqueous dispersion of copolymers or from a melt of copolymers in a hot melt process. The same as in the subsequent drying to evaporate the solvent or water, the drying can be simultaneously applied and the shape stabilization of the PVAL blown film comprises a plasticizer, for example at 80 ° C. The thickness of the adhesive adhesive layer is preferably in the range of from 20 to 1 µm, in particular from 30 to
Jako lepiči adhezní vrstva se podie tohoto vynýle- ,‘4This adhesive layer is preferably, 4
i.i.
- 10 zu s výhodou používaj! Čisté akrylová kopolyméry, které jako podstatnou složku . obsahují monomerní skupiny odvozené od ky%erú kyseliny akrylové nebodá esterá kyseliny methakrylové, dále s výhodou až 10 % hmotnostnioh monomemích skupin odvozených od ethylenicky nenasycenýeh amldd monokarboxylových kyselín se 3 až 5 atómy uhlíku a s výhodou až 5 % hmotnostních moriomerních skupin odvozených od e^thylenicky nenasycenýolj mono karboxylových kyselín se 3 až 5 atómy uhlíku, pŕičemž procen ta jaou vždy vztažena na ^opolymer, nebo popŕipadé se použije výhodné kopolymeru Vinylestéru ' a akrylátu, který jako podstatnou složku o výhodou obsahuje monomerní skupiny otvozené od vinylesterč, jakož i esteru. kyseliny akrylové nebo/a asterú kveelif monomernich skupin ny methakrylové a s výhodou až 5 % hmotnostních/ethylenioky nenasycených kyselín monokarboxylových se 3 až 5 atómy uhlíku, vztaženo^vždy na kopolymér, pŕičemž ve ašech prípadoch teplota tuhnutí kopolymerú je v roztaezí od -50 do -10 °C.- 10 zu preferably use! Pure acrylic copolymers, which as an essential component. contain monomeric groups derived from acrylic acid or non-methacrylic acid esters, further preferably up to 10% by weight of monomer groups derived from ethylenically unsaturated amide of 3 to 5 carbon atoms and preferably up to 5% by weight of ethylene-derived moriomeric groups unsaturated mono-carboxylic acids having 3 to 5 carbon atoms, the percentage being always based on the opolymer, or, where appropriate, a preferred vinyl ester-acrylate copolymer which preferably contains vinyl ester-derived monomer groups as an essential component. acrylic acid and / or Aster kveeli f ny methacrylic monomer units, and preferably up to 5% w / Ethylenically unsaturated monocarboxylic acids having 3 to 5 carbon atoms, each based on ^ a copolymer, wherein in the case ÄŚech pour point of the copolymer is -50 to roztaezí 5 ° C.
Čisté akrylátové kopolyméry obsahují jako monomerní skupiny, s výhodou až 85 $ hmotnostních, zvláätč 75 až 83 % hmotnoatníoh alkylesteru kyseliny akrylové se 4 až 10 atómy uhlíku v alkylové Části, až 20 $ hmotnostních, zvlášté 8 až 17 $ hmotnoatníoh alkyleateru kyseliny methakrylové s 1 až 3 atómy uhlíku v alkylové části, až 10 X hmotnostních, zvlášté 4 až 8 hmotnostních ethylenicky nenasycenáho amidu monokarboxylové kyseliny se 3 až 5 atómy uhlíku aPure acrylate copolymers contain as monomer groups, preferably up to 85% by weight, in particular 75 to 83% by weight, of an alkyl ester of 4 to 10 carbon atoms in the alkyl moiety, up to 20% by weight, especially 8 to 17% by weight of methacrylic acid alkyl ester of 1 up to 3 carbon atoms in the alkyl moiety, up to 10% by weight, in particular 4 to 8% by weight, of ethylenically unsaturated monocarboxylic acid amide having 3 to 5 carbon atoms, and
O až 5 % hmotnostníoh, zvlášté 0,1 až 3 % hmotnostnúch ethylenicky nenasycené monokarboxylové kyseliny ise 3 až 5 atómy uhlíku.0 to 5% by weight, in particular 0.1 to 3% by weight, of ethylenically unsaturated monocarboxylic acids are 3 to 5 carbon atoms.
Viskozita čistého akrylátorého kopolymeru je.v rozraezí od 20 do 80 Pa.a, výhodné od 35 do 50 Pa.s, méreno v taveniné kopolymeru za teploty 180 °0 a teplotu skalného prechodu Tq v rozmezí od -50 do -10 °C.The viscosity of the pure acrylate copolymer is in the range of from 20 to 80 Pa.a, preferably from 35 to 50 Pa.s, measured in the melt copolymer at a temperature of 180 ° C and a rock transition temperature Tq in the range of -50 to -10 ° C.
Jako alkyleBtery kyseliny akrylové se 4 až 10 atómy uhlíku v alkylové části ee používajú sloučeniný s pfímým nebo rozvétvéným-alkylovými zbytkem, s výhodou butyleater, pentylester, hexylester, oktylester, terc.-oktylester, amylester, terc.-aÄylester, 2,2-dimethylbutylester, 3,3-dimethylbutyleeter a 4-ethylhexylester kyseliny akrylové.1Jako alkylestery kyseliny methakrylove se s výhodou pouŽívá methyleeter, ethylester a propylester kyseliny methakrylové, tedy estery e 1 až 3 atómy uhlíku v alkylové části.As alkyl esters of 4 to 10 carbon atoms in the alkyl moiety, compounds having a straight or branched-chain alkyl radical are used, preferably butyl, pentylester, hexyl, octyl, tert-octyl, amyl, tert-butyl, 2,2- dimethylbutyl ester, 3,3-dimethylbutyl ether and acrylic acid 4-ethylhexyl ester. 1 The methacrylic acid alkyl esters are preferably used methyleeter, ethyl and propyl methacrylate esters which E 1 -C 3 alkyl.
Jako ethylenicky nenasycené amidy monokarboxylových kyselin ae 3 až 5 atómy uhlíku se a výhodou používají amid kyselinyakrylové, amid kyseliny methatabylové, amid kyseliny krotonové nebo amid kyseliny vinyloctové.The ethylenically unsaturated amides of the monocarboxylic acids and from 3 to 5 carbon atoms are preferably acrylic acid amide, methabylic acid amide, crotonic acid amide or vinylacetic acid amide.
Jako ethylenicky nenasycené monokarboxylové kyseliny ee 3 až 5 atómy uhlíku se s výhodou používajú kyselina akrylová, kyselina methakrylová, kyselina krotonová nebo kyselina vinylactová.As ethylenically unsaturated monocarboxylic acids having from 3 to 5 carbon atoms, acrylic acid, methacrylic acid, crotonic acid or vinylacetic acid are preferably used.
Výroba čistých akrylátových kopolymeru se mú.že provádét radikálové iniciovanou kopolymeracú raonomerú, s výhodou v organickém rozpouätédle, zpásobem p sobé znáraým. Kopolyméry se mohou získat bezprostredné jako roztoky nebo po odstranSní rozpouštédla jako pevná pryskyrice.The preparation of the pure acrylate copolymers can be carried out by a free-radical initiated copolymerization monomer, preferably in an organic solvent, in a manner known per se. The copolymers can be obtained immediately as solutions or after removal of the solvent as a solid resin.
Kopolyméry vinylesteru a akrylátu obeahují jako monoraemí skupiny s výhodou až 30 % hmotnostních, zvlášté 9,5 až 15 % hmotnoatních vinyltaanokarboxylátu ae 2 až 4 atómy uhlíku v éáati monokarboxylové kyseliny, až 91 % hmotnoatních, zvlášté 80 až 90 '/> hmotnoatních alkylesteru kyseliny akrylové a 4 ažlO atómy uhlíku v alkylová Časti, až 10 £ hraptnostníoh, zvlášté 0,1 až 5 # hmotnostních ethyleniaky nenaaycené monkarboxylové kyaeliny ae až 5 atómy uhlíku.The copolymers of vinyl ester and acrylate contain as monoraemic groups preferably up to 30% by weight, in particular 9.5 to 15% by weight of vinyltaanocarboxylate and 2 to 4 carbon atoms in the monocarboxylic acid, up to 91% by weight, especially 80 to 90% by weight of alkyl ester. acrylic and 4-10 carbon atoms in the alkyl moiety, up to 10%, in particular 0.1-5% by weight, of ethylenically unsaturated monocarboxylic acids and 5 to 5 carbon atoms.
Jako vinylmonokarboxyláty se 2 až 5 atómy uhlíku v části monokax’boxylové kyseliny se s výhodou používají vinylester kyseliny octové, vinylester kyseliny propionové a vinylester kyseliny máselné.As vinyl monocarboxylates having 2 to 5 carbon atoms in the monocoxic acid moiety, vinyl acetate, propionic acid and vinyl butyrate are preferably used.
Jako alkylestery akrylové kyseliny ae 4 až 10 atómy uhlíku v alkylové části se s výhodou používají 2,2-dimethylbutylester, 3,3-dimethylbutyleater, 2-ethylhexyle3<ier nebo zvlášté butylester kyseliny akrylové.As alkyl esters of acrylic acid and from 4 to 10 carbon atoms in the alkyl moiety, preferably 2,2-dimethylbutyl ester, 3,3-dimethylbutyl ester, 2-ethylhexyl ester or a particular butyl ester of acrylic acid are used.
Jako ethylenioky nenesycená monokarboxylové kyseliny se 3 až 5 atómy uhlíku se s výhodou používají kyselinaAs ethylene-unsaturated monocarboxylic acids having 3 to 5 carbon atoms, an acid is preferably used
- 13 akrylová, kyselina met-akrylová, kyselina krotonová nebo kyselina vinyloctová.- 13 acrylic acid, methacrylic acid, crotonic acid or vinylacetic acid.
Výroba kopolymeru vinylesteru a akrylátu se raiže provádét radikálové iniciovanou kopolymeraoí monomeru, s výhodou ve vodné disperzi, podie zpúsobu, který jsou známy jako takové, pŕičemž vodaé disperze kopolymeru mají obsah suôiny s výhodou od 35 do 60 $ hmotnostních, zylástž od 40 do 55 f« hmotnostníoh, vztaženo na vodnou disperzi. Viskozita vodných dieperzí kopolymeru vinylesteru a akrylátu je v rozmezí od 0,1 da 3 Pa.s, s výhodou od 0,2 do 1,5 Pa·», méŕeno za teploty 23 °C v reometru (Contraves-Rheometer STV) podie normy DIN 53 019- Teplota skalného prechodu kopolymerú vinylesteru a akrylátu je v rozmezi od -50 do -10 °C.The preparation of the vinyl ester-acrylate copolymer can be carried out by free-radical initiated copolymerization of the monomer, preferably in an aqueous dispersion, according to a method known per se, wherein the aqueous copolymer dispersions have a dry matter content of preferably from 35 to 60% by weight. By weight, based on the aqueous dispersion. The viscosity of the aqueous dispersions of the vinyl ester-acrylate copolymer is in the range of from 0.1 to 3 Pa · s, preferably from 0.2 to 1.5 Pa · », measured at 23 ° C in a Contraves-Rheometer STV according to standard DIN 53 019 - The rock transition temperature of vinyl ester-acrylate copolymers ranges from -50 to -10 ° C.
Podie vynálezu jsou k výrobč lepičioh adhezníoh vrstev a výhodou vhodné komerčné dostupné čisté akrylátové kopolymery, napríklad v 'Synthacryl typu VSO 2291 (pevný kopolymer) a VSC á292 (60a hmotnostní roztok kopolymeru v iaobutanolu) firmy Hoeehet AG. Oba produkty obsahuj! kopolymer z esterú kyseliny akrylová s teplotou skalného prechodu Τθ -45 °C· Jako xOZpouätédla pro pevné kopolymery se hodí zvláété estery, alkoholy, ketóny, ethery a uhlovodíky, napríklad ethylacetát, pBopylacetát, butylaoetát, aoeton, methylethylketon, ethanol, propanol, ieopropanol, butanol, isobutanol» amylalkohol, dioxan, tetrahydrofurán, halogenované uhlovodíky, jako methylenchlorid, trichlorethylen, perchlorethylen, chlorid uhličitý, uhlovodíky, jako pentan, heaan, cyklohexan, tolaen nebo xylén.According to the invention, commercially available pure acrylate copolymers, for example in Synthacryl type VSO 2291 (solid copolymer) and VSC 292 (60 weight percent copolymer solution in iaobutanol) of Hoeehet AG, are suitable for the production of adhesive layers. Both products contain! copolymers of acrylic esters having a rock-transition temperature of Τθ -45 ° C · Especially esters, alcohols, ketones, ethers and hydrocarbons such as ethyl acetate, p-butyl acetate, butyl acetate, oetone, methyl ethyl ketone, ethanol, propanol, iopropanol are suitable as xo solvents for solid copolymers. butanol, isobutanol »amyl alcohol, dioxane, tetrahydrofuran, halogenated hydrocarbons such as methylene chloride, trichlorethylene, perchlorethylene, carbon tetrachloride, hydrocarbons such as pentane, heaane, cyclohexane, tolaene or xylene.
Obzvlááté výhodný komerčné dostupný kopolymer vi.14 nylesteru a akrylátu ve formé vodná disperz® je napríklad Mowilith LDM 5650 (približná 55# hmotnostní) firmy Hoechst AG, tvorený diaperzí kopolymeru vinylacetátu a esteru kyseliny akrylové, obsahujícího karboxyskupiny. Teplota okelného prechodu Tq kopolymeru činí -32 °G.A particularly preferred commercially available aqueous dispersion (VI.14) butyl ester / acrylate copolymer is, for example, Mowilith LDM 5650 (approximately 55% by weight) from Hoechst AG, formed by a diapolymer of a vinyl acetate / carboxylic acid acrylic ester copolymer. The window transition temperature Tq of the copolymer is -32 ° C.
Jako krycí fólie z plastické hmoty nerozpustné ve vodč a nepropusätné pro vodu a pro vodní páýy ee s výhodou používaj! bSŽná polyolefinové fólie, které jsou za teploty místnosti nerozpustné také v organických rozpuaštédleoh, jako jsou napríklad fólie zhotovené z polyethylenu, ^plypropylenu nebo polyamidu, polyvinylchloridu, polyvinylidenchloridu, polykarbonátu, polyethylentereftalátu a zvlášté biaxiální dloužené polypropylénová fólie. Slouátka krycí fólie z plastické hmoty je s výhodou v rozmezí od 10 do 5Q^im, obzvláôtg od 25 do 35 yim. Zvlášté výhbdné jsou biaxiálnč dloužené polyproj&ylenové fólie o tlouôtce 30 ý1’’’1» ^vláätg pokud jejioh povrch na adhezné kontaktní etrané naoxidován elektrickým oSetfená$ kororpvým . výbojem a tím jsou mu dodány v určitém rozsahu hydrofóbní vlastnosti. Jako zvláät vhodný biaxiálng dloužený komerčné dostupný materiál noibypropylenových fólií ae múže napríklad jmenovRt ^Trespanhan firmy Hoechat AG. V mnohá prípadech múže být výhodné, když se lepiči adhezní vrstva namíato na barierovou fólii pro plyny z o bo u. straň nanese jednostranná na ’ krycí fólii z plastické hmoty nerozpustné ve vodá a vrstvy fólie se analogickým zpúsobem ke spojení kašírují. Pritom rrrilže být zvláätč výhodné a dúležité koronóvé ošetrení adhezní strany krycí fólie pred nanesením lepiči adhezní vrBtvy, a výhodou pri použití polyolefinové fólie.As water-insoluble, water-impermeable and water-impermeable plastic cover films, they are preferably used. Common polyolefin films which are also insoluble at room temperature in organic solvents, such as films made of polyethylene, polypropylene or polyamide, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and especially biaxial stretched polypropylene film. The plastic cover film compound is preferably in the range from 10 to 50 µm, in particular from 25 to 35 µm. A particularly výhbdné the biaxiálnč stretched polyproj & ylene film having 30 characterized tlouôtce 1 '''1 »^ vláätg as jejioh surface of the adhesive contact ETRA naoxidován electric oSetfená $ kororpvým. discharge and hence imparts hydrophobic properties to a certain extent. A particularly suitable biaxially stretched commercially available noibypropylene film material and may be, for example, the name RT-Trespanhan of Hoechat AG. In many cases, it may be advantageous to adhere the adhesive adhesive layer to the gas barrier film. The coating is applied on one side to the water-insoluble plastic cover foil and the layers of the foil are laminated in an analogous manner. Corona treatment of the adhesive side of the cover film before application of the adhesive adhesive layer can be particularly advantageous and important, and preferably when using a polyolefin film.
KaSírování krycí fólie z plastické hmoty s bariero- 15 vou fólií pro plyny, na které je nariesena lepiči adhezní vrstva, se ; múze provádčt pomoci kaSírovecích válcú nebo kalandru za teploty iní i. Cnosti, pMČcmž lisovací tlak válcú s výoodou c Íri í O,} o. ž 1,2 kPa, xvláM o 0,5 až }.,D Wa.The lamination of the plastic cover sheet with the gas barrier sheet onto which the adhesive adhesive layer is deposited is seized; it may be carried out with the aid of transfer rolls or calender at a temperature other than i. 10022004, 10:30:47 Effects of which the pressing pressure is cylindrical with an output of. Wa 1.2 kPa, x lá o 0.5 to 1.00, D Wa.
<v í/icovrstvé fólie podie tohoto vynálezu s ostáva j í s výhodou z alespoň je ’ 1 ľ j Ú bé irííivovJ vrstvy pro plyny obsahujte! vysoko vroucí .!?VAb, na ktoré je oboustrannč nanesená lepiči adbežní vrstva a z o boa straň jsou nakašírovány krycí fólie z plastické hmoty, pŕičemž krycí fólie mohou být stejné nebo rozdílné. V mnohá prípadech muže být výhodná, fólie spojené z více vrstev ka sírová, t o da'l.ší barierovou fólií pro plyny, která je o bo uu t ranne opatrenú lepiči nd.hezní vrstvou, na jednu stranu krycí fólie z plastické hmoty a. tíni získat vícevrstvé fólie se dvema, trend nebo .poprípade včtším ροδtem barierových fólií pro plyny.More preferably, the film of the present invention preferably comprises at least 1% of the gas-containing layer. VAb on which the adhesive adhesive layer is applied on both sides and the plastic cover foils are laminated on both sides, the cover foils being the same or different. In many cases, a multi-layer bonded sulfur film, an additional gas barrier film that is provided with an adhesive layer on one side, on one side of the plastic cover film and may be preferred. It is possible to obtain a multilayer foil with two, trend or possibly higher gas barrier foils.
Celkovú tlouštka fólií spojených z nčko.lika vrstev ý podie tonulo vynálezu ju a výhodou v vozrnezí do 100 do 500 yua, zvláulč od 170 doThe total thickness of the sheets joined from the multiple layers according to the invention preferably in the range from 100 to 500 yuan, in particular from 170 to
PropusCnost vícevrstvýcb fólií podie tohoto vynálezu pro kyslí i: je s výhodou rianáí než 2 cnv’/jn'·. >1. bar pri 93/ re.Lat-ivní vlhkosti, u t úroveň o podie normy Π1Ν 5 J j80 a menší ne z o,j. ωπ·\Α1 . d. bur pri relatívni vlhkosti' 53 staro-,/ veno pocle lóže normy. Vícovrstvé fólie podie vynálezu mohou být trariofiarentní. až opakní, prúsvitné ' nebo neprúhledné. pigment o vaní· neho vybarvené, když s e napríklad du bariprové fólie pro plyny poprípade vnešou pigmenty, ktere se mohou vybervi. t, nebo ho r vi W. V í e evrstvé fólie podie tohoto vynálezu se mohou t ermop takticky formovat,'s-výhodou zpracovávat, s var e t nebo uzavírat na obal, .y, zvlášt? ha fóliové pytle e kromé toho stejné tak riepoškoditelnč ohráplt pri potisku na vnitŕni plose vrstvy. I , \ \ á \ \The oxygen permeability of the multilayer films of the present invention is preferably less than 2 cm 3 / min. > First bar at 93 / re.Lat.-humidity, u t level o according to standard Π1Ν 5 J j80 and less than o, j. ωπ · \ Α1. d. bur at a relative humidity of '53 old -, / veno pocle box standard. The multilayer films of the invention may be tri-transparent. opaque 'translucent' or opaque. a pigment on the tub is colored when, for example, the gas foil films or the outer pigments which may be colored may be colored. The multi-layer films of the present invention may be tactically formed, preferably processed, boiled or sealed, especially, in particular. In addition, foil bags are also the same so that they can be damaged by printing on the inner surface of the layer. I, \ \ á \ \
, \, \
Λ \Λ \
- 16 Bícevrstvé fólie podie tohoto vynálezu je možné s výhodou používal k balení nebo potahování vét&ího počtu produktá zahranújícímu proníkání pôdy a plynu, obzvlášté kyslíku, vodních par, aromatických látek a popáípadé rozpaučtédel. ľakovýml produkty jsou napríklad potraviny, zejména napríklad produkty citlivá na kyslík, jako jsou ryby a uzeniny, rybí produkty, káva, majonéza, jedlé oleje, vitamíny, hluboko mražená strava, nápoje, korení, aromatické látky, kosmetické prcetŕedky, léčiva, chemikálie, popŕipadé organická rozpouätédla, jako je benzín, benzen, ethery, estery, ketóny, mánerální oleje, tuky, stejnč jakovyložení zračíoh komor pro Čerstvé ovoce aoiody. 'The bi-layered films of the present invention may be advantageously used to package or coat a greater number of products to infiltrate soil and gas, particularly oxygen, water vapor, flavorants and, if appropriate, diluents. for example, food products, in particular oxygen-sensitive products such as fish and sausages, fish products, coffee, mayonnaise, edible oils, vitamins, deep-frozen foods, drinks, spices, flavorings, cosmetics, pharmaceuticals, chemicals, organic solvents such as gasoline, benzene, ethers, esters, ketones, mercury oils, fats, as well as linings of fresh fruit and iodine chambers. '
Príklady provedení vynálezuDETAILED DESCRIPTION OF THE INVENTION
Vynález je objasnčn príklady, které jsou uvedený dále ·The invention is illustrated by the following examples.
Príklad 1Example 1
A) Výroba barierové fólie pro plyny z PVAL obsahujicí zmSkčovädlo s oboustrannou lepiči adhezní vrstvouA) Production of PVAL gas barrier foil containing plasticizer with double sided adhesive layer
V zaŕízení a ručeným mícháním, které je analogické jako v pŕíkladč 5 evropekého patentu č. 0 040 587, se vyrobí plastlfikovený granulát euché amSsi s PVAL, obsahujíoí zmékčovadlo, z téchto složek:In a device and a stirring mixer analogous to Example 5 of European patent no. 0 040 587, a plasticized plasticized euché amSsi granule with PVAL is prepared, containing a plasticizer, from the following components:
1000 dílu hmotnostnícíi Mowiol 28-99^1000 parts by weight Mowiol 28-99 ^
180 dílň hmotnostních glycerín180 workshop weight glycerin
100 dílu hmotnostních100 parts by weight
100 dílu hmotnootních dílu hmotn o utri í ch voda100 parts by weight of wiped water
PráŠek Mowilith PS2^Powder Mowilith PS 2 ^
Aerosi I.Aerosi I.
Mowiol 28-99 je oocr.odnč dostupný, grnnulovaný, vysoko vroucí ľ'VA‘L s po tymci-ucním s t u p n č- m 0.?^ 2000, jwhož stupeň zraýdelnení odpovídá 99,-1 A rnolárním, jehož esterové číslo je 8 mg KOíi/g, který obsahuje u ,5 c unotnostníno zbytkovýou acctylovýcL skupín o jehož viskozita v nmotnostnč 4% vodném roztoku sa teploty ?0 °·:: odpovídá 28 mPa.s, mčŕeno podie normy DTN 53 015.Mowiol 28-99 is a commercially available, high-boiling, high-boiling liquid having a titration degree of 0.? 2000, whose degree of saponification corresponds to 99, -1 A rnolar, the ester number of which is 8; mg Kg / g, containing 0.5% by weight of residual acetyl groups having a viscosity in a 4% by weight aqueous solution and a temperature of 0 ° C corresponding to 28 mPa · s, measured according to DTN 53 015.
'·' Prášok Mow.í litb D3 ja práškový hortopolymerní a ve voclč znovu diapergovhtclný polymér· polyvinylocetátu, vyrobený rozstrikovácím rušením vodné diaperze polyvinylacetátu.Powder Mow lit3 D3 is a powdered, hydrocopolymer and again diapergeable polyvinyl acetate polymer produced by the spattering of the aqueous dispersion of polyvinyl acetate.
>) ' žxrcnil je vysoou disperzní, synteticky vyrobenáIt is a high dispersion, synthetically produced
V J :V J:
zme kčovtu',1 1·.^ v vy ť u kov.-:1011)1 e: za obvyklých teplôt fólii o ťLouutoc -!5 po. oodlažení r a tep a v ý s 1 c d 11 á f ‘ o 1. i. e zaŕízení k ukládΛηi oboustranné nanc ledný prnnujál Y'Vlľ, suché smési planí i. C i.kované m ;:1u.vi.£,e zpracúje truderu opál ŕonéro z n .r ízenfni pro be žnýr'i um a obvodu Ώ?The metal is 100%, at 100 ° C, at 100 ° C. oladla ra r a r s s 1 cd 11 á f 'o 1. i. e equipment for storing double-sided nanc ice lining Y'Vlľ, dry mixes i. C i.kované M: £ 1u.vi., Twin Screw extruder treated much opal stamps Roner, R ízenfni žnýr'i to be m and the circuit Ώ?
/ í/ í
i o tu mistnosti ú úver ii.r íl·!.!, i ŕ'i <? ťo’l. í e do povríJ en í lepiči ad n e zvi í obsahujici v jecJriošnekovérn odvádehí plynú zpusobem na jukontní vyťť0covanou ibližnč 160 cm, Ľaclice se rozrízne v nodólném; smčrui o tu rooms ú loan ii.r ile ·!.! i i''<?ťo'l. that the glue and the admixture containing the yoghurt drains flow to a pulverized, approximately 160 cm thick, cut in a nodole; SMČR
160 cm ae zavádí preš tvovaoího prístroje \pro vrstvy. V povrstvovkcím160 cm and introduces a preforming machine for layers. V povrstvovkcím
- 18 frí sta® j i fólie prochází párem nanáéecích válcu a pŕátom dochází k oboustrannému rovnomernému nanášení adhezní vrstvy ve formô vodné disperze plastická hmoty. Jako dieperze plastické hmoty se používa nezŕedéný Mowiiith LDW 5650, približné hmotnostné 55X- disperze kopolyméru vinylacetátu a esteru kyseliny akrylovó obsahujícího karboxyskupiny, kde pódií kopolyméru má teplotu 3kelného prechodu 'ľ/, odpovídající -32 °C. V dále zarazeném oučícím kanále probšhne vysuSení disperzní vrstvy a unížení obsahu vody ve fólii na méné než 5 Á hmotnostních, vztaženo na PVAL, jakož i současné rozmerovému vyrovnání fólie jejím tepelným zpracovánim pri teploté 80 °C.18 sheets of film are passed through a pair of rollers and, on the other hand, the adhesive layer is applied on both sides in the form of an aqueous plastic dispersion. As the plastic dispersion, undiluted Mowiiith LDW 5650, an approximate 55% by weight dispersion of vinyl acetate copolymer and acrylic acid ester containing a carboxyl group, is used, wherein the copolymer stage has a 3-glass transition temperature ľ 1, corresponding to -32 ° C. In the downstream learning channel, the dispersion layer is dried and the water content of the film is less than 5 Å by weight based on PVAL, as well as simultaneous dimensional alignment of the film by heat treatment at 80 ° C.
B) Výroba vícevrstvé fólie ti bnrierovými vlastnostmi pro plynyB) Production of a multilayer foil with three-gas properties
PVAL barierová fólie pro plyny obsahujici zmékčovadlo a obousbranné povrstvená samolapícími adbezními vrstvami o tlouätce vždy približné 35 /im, která 3e ne oh a la tvarovéPVAL gas barrier foil containing plasticizer and two-sided coated with self-adhesive adhesion layers of a thickness of approximately 35 µm each and which is not shaped
Z ustálit v susícíia kanále podie príkladu 1A, se ochladí na teplotu místnosti a. na kalandru oboustrannč kašíruje s obchodné dostupnou trespapimnovou fólií, ve vodé nerozpustnou, biaxiálné dlouženou a na kaMírovací etrané dodatočné koronové ; zpracovanou polypropylenovou fólií o tlouStce 30 ^juh, která je nerozpustná v.organických rozpouétédleeh za teploty místnosti, pŕičemž ae použije lisovací tlak na váloích 600 kPa.Výsledná vícevratvá fólie má tlcfetku približné 1702*® a je prúhledná, mčkká, prumémé flexibilní, termoplasticky formováteiná a schopná opocení, je jí možné uzavŕít ŕ a je potisknutelná. Irostupnost vícevrstvé fólie pro kyslík činí 0,2 cmVm^.d.bar pri relatívni vlhkosti 53 ť» a 1,4Z stabilize in the drying channel of Example 1A, cool to room temperature and. it is laminated on both sides with commercially available Trespapim foil, water-insoluble, biaxially stretched and additional corona coated on the calender; treated polypropylene film having a thickness of 30 .mu.m, which is insoluble in organic solvents at room temperature using a compression pressure of 600 kPa. The resulting multilayer film has a thickness of approximately 1702 * ® and is a transparent, soft, flexible, thermoplastic flexible mold. and capable of sweating, it can be closed and printed. The availability of the multilayer oxygen film is 0.2 cmVm @. D.bar at relative humidity of 53 " and 1.4.
- 19 3 2 cm /m .d.bar pri relatívni vlhkosti 93 /, mčženo vždy podie normy D IN 53 3β0·- 19 3 2 cm / m .d.bar at relative humidity 93 /, measured according to D IN 53 3β0 ·
Ve výäe uvedením rozmaru jednotky proetupnost pro kyslík znamená n vyjadruje pročlé množství kyslíku, nT označuje pLochu fólie v metroch cteerečních, d označuje sledovanou dobu vyjádrenou ve dnech a bar označuje parciálni tlak kyslíku, podie citované normy vyjádžený v táto jednotce.In the above, the capability of the unit of oxygen permeability means n denotes the total amount of oxygen, nT denotes the surface area of the foil in meters, d denotes the observed time expressed in days and bar denotes the partial pressure of oxygen, according to the cited standard expressed in this unit.
Claims (8)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4123127A DE4123127C2 (en) | 1991-07-12 | 1991-07-12 | Multi-layer composite film with improved gas barrier effect |
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| SK216292A3 true SK216292A3 (en) | 1993-11-10 |
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| SK2162-92A SK216292A3 (en) | 1991-07-12 | 1992-07-10 | Multilayer foil with improved barrier effect for gases |
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| US (1) | US5324572A (en) |
| EP (1) | EP0524486A1 (en) |
| JP (1) | JPH0679833A (en) |
| CA (1) | CA2073653A1 (en) |
| CZ (1) | CZ216292A3 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19721142A1 (en) * | 1997-05-21 | 1998-11-26 | Kalle Nalo Gmbh | Multi-layer, biaxially stretched food casing with two oxygen barrier layers |
| AT408631B (en) * | 1999-09-22 | 2002-01-25 | Teich Ag | AROMADICHT RESealable PACKAGING FOR DRY PACKAGING GOODS |
| DE20200085U1 (en) | 2002-01-04 | 2002-03-28 | Nordenia Deutschland Gronau GmbH, 48599 Gronau | Packaging for mineral oils |
| US20030143380A1 (en) * | 2002-01-31 | 2003-07-31 | Paul Jonathan P. | Visible light energy emitting laminate for use in food packaging and method of producing |
| DE20217987U1 (en) * | 2002-06-20 | 2003-03-06 | Kuhne Anlagenbau GmbH, 53757 Sankt Augustin | Multi-layer, flat or tubular food casing or film |
| ITMI20022156A1 (en) * | 2002-10-11 | 2004-04-12 | Polifilms Srl | HEAT-SHRINK MULTILAYER FILM WITH GAS BARRIER PROPERTIES. |
| DE10254172B4 (en) * | 2002-11-20 | 2005-07-21 | Kuhne Anlagenbau Gmbh | Multilayered, surface or tubular food casing or film |
| CA2525622C (en) * | 2003-05-16 | 2010-10-26 | Toppan Printing Co., Ltd. | Transparent gas barrier laminated film, and electroluminescent light-emiiting element, electroluminescent display device, and electrophoretic display panel using the same |
| US7829147B2 (en) | 2005-08-18 | 2010-11-09 | Corning Incorporated | Hermetically sealing a device without a heat treating step and the resulting hermetically sealed device |
| US20070040501A1 (en) | 2005-08-18 | 2007-02-22 | Aitken Bruce G | Method for inhibiting oxygen and moisture degradation of a device and the resulting device |
| US7722929B2 (en) * | 2005-08-18 | 2010-05-25 | Corning Incorporated | Sealing technique for decreasing the time it takes to hermetically seal a device and the resulting hermetically sealed device |
| DE102005051370A1 (en) * | 2005-10-25 | 2007-04-26 | Wipak Walsrode Gmbh & Co.Kg | Thermoformable multilayer foil for packaging tray, has polyolefin layer(s) formed from thermoplastic polyolefin and/or olefin copolymer, and gas barrier layer(s), and has preset oxygen transmission |
| JP2008008486A (en) | 2006-05-31 | 2008-01-17 | Tokai Rubber Ind Ltd | Refrigerant transportation hose |
| US20080044635A1 (en) * | 2006-06-08 | 2008-02-21 | O'neill Michael | Barrier film for flexible articles |
| JP2008105395A (en) * | 2006-09-27 | 2008-05-08 | Denso Corp | Refrigerant transporting hose and manufacturing method therefor |
| US8115326B2 (en) | 2006-11-30 | 2012-02-14 | Corning Incorporated | Flexible substrates having a thin-film barrier |
| KR100855783B1 (en) * | 2007-03-13 | 2008-09-01 | 엘에스엠트론 주식회사 | Method for dying polyimide film to increasing the adhesion between metal and the polyimide film |
| US7874731B2 (en) | 2007-06-15 | 2011-01-25 | S.C. Johnson Home Storage, Inc. | Valve for a recloseable container |
| US7887238B2 (en) | 2007-06-15 | 2011-02-15 | S.C. Johnson Home Storage, Inc. | Flow channels for a pouch |
| US7857515B2 (en) | 2007-06-15 | 2010-12-28 | S.C. Johnson Home Storage, Inc. | Airtight closure mechanism for a reclosable pouch |
| US7946766B2 (en) | 2007-06-15 | 2011-05-24 | S.C. Johnson & Son, Inc. | Offset closure mechanism for a reclosable pouch |
| US7967509B2 (en) | 2007-06-15 | 2011-06-28 | S.C. Johnson & Son, Inc. | Pouch with a valve |
| ITVA20090027A1 (en) * | 2009-04-17 | 2010-10-18 | Masterpack S P A | COUPLED WITH PAPER AND AT LEAST TWO DEGRADABLE PLASTIC FILMS WITH HUMIDITY AND OXYGEN BARRIER AND THERMO-HEATED PACKAGING BAGS |
| KR20130097176A (en) * | 2010-08-10 | 2013-09-02 | 에셀 프로팩 리미티드 | Multi-layer sheet and method thereof |
| CA2748936C (en) * | 2010-08-16 | 2016-10-11 | George M. Orlych | Self-adhered single-sided slip-resistant material |
| CN107953623A (en) * | 2011-11-04 | 2018-04-24 | 琳得科株式会社 | Gas barrier film and its manufacture method, gas barrier film stack, use for electronic equipment component and electronic device |
| US20150037915A1 (en) * | 2013-07-31 | 2015-02-05 | Wei-Sheng Lei | Method and system for laser focus plane determination in a laser scribing process |
| CN111016118B (en) * | 2019-12-25 | 2021-08-24 | 山东亚新塑料包装有限公司 | Antibacterial high-oxygen barrier PE composite membrane and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0004587B1 (en) * | 1978-03-23 | 1983-02-09 | Hoechst Aktiengesellschaft | Polyvinyl alcohol pellets containing a plasticizer, and method for their preparation |
| US4239826A (en) * | 1978-12-28 | 1980-12-16 | American Can Company | Multi-layer barrier film |
| DE3039386A1 (en) * | 1980-10-18 | 1982-05-27 | Hoechst Ag, 6000 Frankfurt | METHOD FOR CHANGING THE WATER CONTENT OF WATER-ABSORBING OR WATER-REPELLENT MATERIAL |
| JPS5894432A (en) * | 1981-11-28 | 1983-06-04 | バスフ アクチエンゲゼルシヤフト | Manufacture of plane-shaped shape from vinyl alcohol polymer |
| WO1983003205A1 (en) * | 1982-03-12 | 1983-09-29 | Henning Risvig Henriksen | Protective garment |
| US4448622A (en) * | 1982-04-26 | 1984-05-15 | The United States Of America As Represented By The United States Department Of Energy | Composite polymeric film and method for its use in installing a very thin polymeric film in a device |
| DE8214634U1 (en) * | 1982-05-19 | 1982-09-02 | Hoechst Ag, 6000 Frankfurt | LAYERING MATERIAL BASED ON A WOOD VENEER |
| DE3306189A1 (en) * | 1983-02-23 | 1984-08-23 | Hoechst Ag, 6230 Frankfurt | MULTILAYER FILM WITH A GAS AND AROMA BARRIER, METHOD FOR THEIR PRODUCTION AND THEIR USE |
-
1991
- 1991-07-12 DE DE4123127A patent/DE4123127C2/en not_active Expired - Fee Related
-
1992
- 1992-07-08 EP EP92111546A patent/EP0524486A1/en not_active Withdrawn
- 1992-07-10 CA CA002073653A patent/CA2073653A1/en not_active Abandoned
- 1992-07-10 CZ CS922162A patent/CZ216292A3/en unknown
- 1992-07-10 US US07/911,913 patent/US5324572A/en not_active Expired - Fee Related
- 1992-07-10 SK SK2162-92A patent/SK216292A3/en unknown
- 1992-07-10 JP JP4184149A patent/JPH0679833A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE4123127C2 (en) | 1996-06-20 |
| US5324572A (en) | 1994-06-28 |
| CA2073653A1 (en) | 1993-01-13 |
| DE4123127A1 (en) | 1993-01-14 |
| CZ216292A3 (en) | 1993-01-13 |
| EP0524486A1 (en) | 1993-01-27 |
| JPH0679833A (en) | 1994-03-22 |
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